Vulcanizable polymeric compositions containing a zinc dimethacrylate adjuvant and method for preparing the adjuvant

ABSTRACT

Vulcanizable polymeric compositions comprising certain rubbery polymers or polymer blends, a zinc dimethacrylate adjuvant having a surface area of from about 3.7 to about 5.4 m 2  /g or more and a peroxide curing agent are provided. Polymeric compositions which contain 25 parts by weight or more of the zinc dimethacrylate adjuvant per 100 parts by weight of rubbery polymer in the absence of reinforcing fillers exhibit excellent strength and hysteresis characteristcs when cured. The surface area of the zinc dimethacrylate adjuvant along with its method of preparation are extremely important factors in the excellent properties obtained when polymeric compositions containing the adjuvant are cured.

CROSS REFERENCES TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 653,177,filed Nov. 7, 1984, now abandoned, which is a continuation-in-part ofU.S. application Ser. No. 421,012, filed Sept. 21, 1982, now abandoned.

BACKGROUND OF THE INVENTION

The invention relates to vulcanizable polymeric compositions containinga zinc dimethacrylate adjuvant and to a method of preparing theadjuvant. More particularly, the invention relates to vulcanizablepolymeric compositions comprising certain rubbery polymers or polymerblends, a zinc dimethacrylate adjuvant having specified surface arealimitations and peroxide curing agents, and to a method of preparing thezinc dimethacrylate.

Various patents and publications describe the preparation of metallicsalts of methacrylic acid.

Thus, Japan Kokai 76,138,616 relates to the preparation of zincdimethacrylate and zinc diacrylate by a process which involves reactingacrylic or methacrylic acid with zinc oxide or zinc hydroxide at40°-100° C. in water insoluble hydrocarbon solvents mixtures in whichthe hydrocarbon solvent forms an azeotrope with water, removing thewater by azeotropic distillation and drying the resultant product.Hydrocarbon solvents which are disclosed include benzene, toluene,xylenes, cyclohexane, methylcyclohexane, n-heptane, n-hexane, etc.

U.S. Pat. No. 4,082,288 relates to the preparation of basic zincmethacrylate by milling under agitation methacrylic acid with asuspension of zinc oxide in a liquid medium such as water or a volatileorganic liquid.

U.S. Pat. No. 4,100,182 relates to a method for preparing an adjuvantfor an elastomeric composition which involves mixing methacrylic acidwith zinc oxide in a liquid medium in the proportions required to formbasic zinc methacrylate, removing the liquid medium and finely dividingthe resulting reaction product. The reference teaches that the molarratios of zinc oxide to methacrylic acid used in forming the reactionproduct is ordinarily at least 0.8 to 1, preferably 2 to 1 (column 2lines 18-30); that the lliquid medium may be water or a volatile organicliquid such as a hydrocarbon liquid or an alkanol (column 2 lines 45-48)and that the reaction product should be finely powdered to at least afineness sufficient to pass a 200 mesh sieve preferably a 300 meshsieve.

U.S. Pat. No. 4,191,671 apparently discloses the in-situ preparation ofzinc methacrylate by a process which involves first mixing a rubberypolymer such as polybutadiene with methacrylic acid, then adding zincoxide thereto in a standard kneader and mixing to obtain a homogeneousrubber composition.

U.S. Pat. No. 4,266,772 discloses the preparation of basic zincmethacrylate using the same process described in U.S. Pat. No.4,082,288. The acricle entitled "Elastic Properties and Structures ofPolybutadiene Vulcanized With Magnesium Methacrylate" appearing in theJournal of Applied Polymer Science, Vol. 16, pages 505-518 (1972) atpage 505 states magnesium methacrylate utilized therein was prepared byheating aqueous solutions of the acid and magnesium hydroxide and thenpassing the salt through a sieve to obtain salt particles having adiameter of less than 0.5 millimeters.

In addition, various patents and publications describe vulcanizablepolymeric compositions containing metallic salts of methacrylic acid.

Thus, U.S. Pat. No. 3,823,122 relates to curable SBR or neopreneelastomer compositions containing from 1 to 15 parts by weight per 100parts by weight of elastomer of a substituted acrylic acid or acid salt,with the preferred acid salt indicated to be zinc methacrylate which isdescribed as being formed by merely reacting sodium methacrylate withzinc chloride. Elastomer compositions which are disclosed include areinforcing filler such as carbon black but do not include a peroxidecuring agent.

U.S. Pat. No. 4,082,288 discloses free-radial cross-linkable elastomercompositions containing a peroxide cross-linkable elastomer, from 10 toabout 60 parts by weight per 100 parts by weight of elastomer of basiczinc methacrylate, a peroxide curing agent and optionally reinforcingfillers such as litharge or zinc oxide in amounts of 2 to 10 parts byweight per 100 parts by weight of elastomer.

U.S. Pat. No. 4,191,671 relates to curable rubber compositionscomprising (A) a diene elastomer, (B) an alpha-beta ethylenicallyunsaturated carboxylic acid, wherein the ratio by weight of component(A) to component (B) is 87/13 to 55/45, (C) a divalent metal compoundbeing present in quantities of 50 to 150 parts by weight per 100 partsby weight of component (B), and (D) an organic peroxide being present inquantities of 0.3 to 5.0 parts by weight per 100 parts by weight of thecombined weight of components (A) and (B). The compositions mayadditionally contain an unpolymerizable carboxylic acid, carbon black inamounts of less than 50 parts by weight per 100 parts by weight ofelastomer and an amine and/or phenol compound.

U.S. Pat. No. 4,192,790 relates to elastomer compositions having reducedMooney viscosity in the compounded state. The Mooney viscosity of theelastomer compositions are reduced by the incorporation therein of from0.1 to 7.0 parts by weight of basic zinc methacrylate per 100 parts byweight of elastomer. In addition to the basic zinc methacrylate, theelastomer compositions contain various elastomers or elastomer blends,an inorganic particulate filler and optionally carbon black (20 to 150parts per 100 parts elastomer) and curing agents such as peroxidecuratives.

U.S. Pat. No. 4,266,772 relates to solid golf balls formed from acurable elastomer composition comprising a free-radical crosslinkableelastomer, especially a peroxide cross-linkable elastomer, basic zincmethacrylate (about 10 to about 60 parts by weight per 100 parts byweight of elastomer) and a curing agent such as a peroxide curing agent.The compositions may optionally contain reinforcing fillers such aslitharge or zinc oxide in amounts of for example 2 to 10 parts per 100parts of elastomer.

British Pat. No. 1,091,818 discloses vulcanizable compositionscomprising alpha-olefin polymers and a curing system consisting of metalsalts of acrylic acid or methacrylic acid in amounts of from 1 to 10parts of metal salt per 100 parts of polymer and an organic peroxide.The compositions may additionally contain reinforcing agents and fillerssuch as carbon blacks, metal oxides, etc.

British Pat. No. 2,042,553 discloses crosslinked cellular elastomericcompositions which are formed from an elastomer composition comprising anatural and/or synthetic rubber, a crosslinking agent such as aperoxide, a monomeric metallic salt such as zinc dimethacrylate, zincdiacrylate, preferably basic zinc methacrylate and a blowing agent. Thecompositions may additionally contain fillers such as carbon black ortitanium dioxide and other known compounding additives.

The article entitled "Vulcanization of Rubbers By Salts of UnsaturatedAcids. Vulcanization of Butadiene-Styrene Rubber By Methacrylate Salts"by A. A. Dontsov et al. appearing in the Colloid Journal USSR, Volume31, pages 293-297 (1969) discloses vulcanizable compositions comprisingbutadiene-styrene rubber or ethylene-propylene rubber, magnesiummethacrylate or sodium methacrylate and dicumyl peroxide.

The article entitled "Elastic Properties and Structure of PolybutadieneVulcanized with Magnesium Methacrylate" by A. Dontsov et al. appearingin the Journal of Applied Polymer Science, Volume 16, pages 505-518(1972) discloses vulcanizable compositions comprising polybutadiene,magnesium methacrylate and dicumyl peroxide.

The article entitled "General Regularities of HeterogeneousVulcanization" by A. A. Dontsov appearing in the publication Rubbercon'77, International Rubber Conference, Volume 2, pages 26-1 through 26-12(1977) discloses vulcanizable compositions comprising styrene-butadienerubber or ethylene-propylene rubber; magnesium, sodium, zinc and cadmiumsalt of methacrylic, maleic and betaphenyl acrylic acids and radicaltype initiators such as dicumyl peroxide.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the invention, a method forpreparing a zinc dimethacrylate powder having a surface area of fromabout 3.7 to about 5.4 m² /g or more is provided. The method generallyinvolves first reacting under agitation zinc oxide and methacrylic acidin an amount of from about 0.5 to about 0.6 moles of zinc oxide per moleof methacrylic acid in a liquid aliphatic hydrocarbon dispersing mediumto produce particles of zinc dimethacrylate in the liquid medium. Then,the particles of zinc dimethacrylate are recovered from the liquidmedium and dried to produce the zinc dimethacrylate powder.

In a further embodiment of the invention, vulcanizable polymericcompositions are provided which comprise (a) rubbery polymers selectedfrom the group consisting of natural rubber, ethylene/propylenecopolymers, ethylene/propylene/diene terpolymers, styrene/butadienecopolymers, nitrile rubbers, neoprene and blends thereof; (b) from about25 to about 85 parts by weight per 100 parts by weight of said rubberypolymers of said zinc dimethacrylate having a surface area of from about3.7 to about 5.4 m² /g or more; and (c) a cure effective amount of aperoxide curing agent. Such polymeric compositions exhibit excellentstrength and hysteresis characteristics in the cured state.

DETAILED DESCRIPTION OF THE INVENTION

To prepare the zinc dimethacrylate powder, the zinc oxide andmethacrylic acid are first brought together in a liquid aliphatichydrocarbon dispersion medium which aids in dissipating the heat that isliberated by the exothermic reaction of the two materials. Preferably,the zinc oxide is first dispersed in the liquid medium and themethacrylic acid is then added to the dispersion while agitating. Fromabout 0.5 to about 0.6 moles of zinc oxide per mole of methacrylic acidare employed in the reaction.

Various liquid aliphatic hydrocarbons may be utilized as the liquiddispersion medium. However, it is preferred to utilize an alkane as theliquid dispersion medium and of the alkanes, hexane is especiallypreferred. A surprising aspect of the use of hexane as the dispersionmedium is the finding that the zinc dimethacrylate powder produced byreaction in the hexane medium consistently exhibits the desired surfacearea characteristics even under varying conditions of agitation.

While not essential, it is generally preferred to include a small amountof a nonionic surfactant in the dispersion medium as this aids inproducing a fluid suspension which is pumpable and pourable. Variouswell known nonionic surfactants can be utilized for that purposeincluding silicone type surfactants and alkylaryl polyether alcoholtypes. Preferred nonionic surfactants are the alkylaryl polyetheralcohols.

Amounts of nonionic surfactant included in the dispersion medium mayrange from about 0.1 to about 1.0%, preferably 0.3 to 0.5% by weightbased on the combined weight of zinc oxide and methacrylic acid.

The reaction between the zinc oxide and methacrylic acid is preferablyconducted at room at ambient temperature (i.e., no added heat), underagitation and in the presence of the nonionic surfactant. This preferredreaction procedure produces a fluid suspension which as indicated aboveis both pumpable and pourable. If desired, the reaction can be conductedat temperatures of up to about 70° C. and without a surfactant. In thislatter case, a slurry or thick paste is obtained which does not pourwell. However, this procedure though not preferred, does not appear todegrade the finished product.

Reaction times may vary considerably depending on factors such as batchsize, degree of agitation and the like. In general, reaction times mayrange from about 4 to about 20 hours or more.

In the preferred embodiment, as the reaction between the zinc oxide andmethacrylic acid nears completion, the product takes on the form of afluid suspension of zinc dimethacrylate particles in the liquid medium,whereas when the reaction is conducted at higher temperatures andwithout surfactant, the product takes on the form of a slurry of zincdimethacrylate particles in the liquid medium.

In any event, the second step in the method is to recover the particlesof zinc dimethacrylate from the liquid medium. This can be accomplishedby any convenient method. Thus, for example, the zinc dimethacrylateparticles may be recovered by filtration (which is preferred) or byremoval of the liquid medium as by evaporation. When the zincdimethacrylate particles are recovered by filtration, it is oftendesirable and preferred to remove additional portions of the liquidmedium by pressing the particles.

Following the recovery step, the zinc dimethacrylate particles are driedto produce the zinc dimethacrylate powder. Drying can be accomplished byany conventional method. Thus, air drying and/or vacuum drying can beutilized. It is often preferred to first air dry the particles and thenvacuum dry in an oven at temperatures of from about 60° C. to about 70°C.

The zinc dimethacrylate product at this point is in the form of alightly caked powder. If desired, the product can be used in that formas an adjuvant in compositions of the invention with good results.However, it is generally preferred to break up the lightly caked powderfor ease of handling and blending with the rubbery polymers and othercomponents to prepare the compositions of the invention. This can beaccomplished in any known manner. Thus, for example, the lightly cakedpowder can be broken up by a suitable blender such as a Waring blender.While not essential, it is usually desirable and preferred to remove anyexceptionally large particles from the powder by passing the powderthrough an appropriate sieve such as, for example, a number 50 meshscreen.

The zinc dimethacrylate product prepared in accordance with the aboveprocess generally has an ash content of from about 30 to about 35percent.

Rubbery polymers which may be utilized as component (a) in thecompositions of the invention include natural rubber; ehtylene/propylenecopolymers; ethylene/propylene/diene terpolymers in which the dienecomponent is a non-conjugated diene such as 1,4-hexadiene,dicyclopentadiene, 5-ethylidene-2-norbornene and the like;styrene/butadiene copolymers (i.e., SBR), nitrile rubber, neoprene andblends or mixtures thereof.

One of the surprising and unexpected aspects of the composition of theinvention has been the discovery that the use of the zinc dimethacrylateand peroxide components permits the cure of rubbery polymer blends whichare normally regarded as "cure incompatible." For example, it has beenfound that compositions containing blends of EPDM and nitrile rubbercure well and exhibit excellent strength.

Another surprising aspect of the compositions of the invention is thediscovery that compositions containing ethylene/propylene rubber whichcontains no unsaturation also cure well and exhibit good strengthcharcteristics.

The zinc dimethacrylate utilized as component (b) of the composition isas indicated a zinc dimethacrylate powder having a surface area of fromabout 3.7 to about 5.4 square meters per gram (m² /g) or more and an ashcontent of from about 30 to about 35 percent. The zinc dimethacrylate isprepared in accordance with the process described above.

Amounts of zinc dimethacrylate employed may range from about 25 to about85 parts by weight per 100 parts by weight of rubbery polymers withpreferred amounts being from about 50 to about 80 parts by weight per100 parts by weight of rubbery polymers. Compositions containing 25parts by weight of zinc dimethacrylate or more when cured exhibit muchlower hysteresis than conventional carbon black reinforced rubbers.Compositions containing 50 parts by weight of zinc dimethacrylate ormore when cured exhibit excellent strength characteristics (e.g.,modulus, elongation and break strengths) approaching the properties ofhigh quality polyurethanes.

Peroxide curing agents which may be used as component (c) includeorganic peroxides such as dicumyl peroxide, bis-(t-butylperoxy)diisopropyl benzene, t-butyl perbenzoate, di-t-butyl peroxide,2,5-dimethyl-2,5-di-t-butyl peroxy-hexane and the like. The preferredperoxide curing agents are bis-(t-butyl peroxy)diisopropyl benzene anddicumyl peroxide.

Amounts of peroxide curing agents included in the compositions willdepend upon the type rubber utilized and may generally be stated as cureeffective amounts. In general, such amounts may range from about 0.2 toabout 2.0 parts by weight per 100 parts by weight of rubbery polymer.

The compositions may optionally contain other conventional additiveswhich are commonly utilized in rubber compositions. Such additives mayinclude reinforcing agents and fillers such as carbon blacks, clays,silicas and calcium carbonate, process and extender oils, antioxidants,waxes, placticizers and the like. When it is desired to include suchreinforcing agents and fillers in the compositions, these may generallybe utilized in amounts of from about 5 to about 60 parts by weight per100 parts by weight of rubbery polymers. Other additives may be employedin amounts conventionally used in standard rubber compounds.

The rubber compositions may be prepared by any conventional proceduresuch as, for example, by mixing the ingredients in an internal mixer oron a mill.

The following examples are submitted for the purpose of furtherillustrating the nature of the present invention and are not intended asa limitation on the scope thereof. Parts and percentages referred to inthe examples and throughout the specification are by weight unlessotherwise indicated.

The following examples (i.e., 1-5) illustrate the preparation of zincdimethacrylate by the process of the invention.

EXAMPLE 1

To each of fifteen (15) 28-ounce beverage bottles were charged 300 gramsof hexane. Then 37.5 grams of zinc oxide, previously passed through anumber 50 mesh screen were added to the bottles with swirling. Followingthis addition, 77.5 grams of methacrylic acid were added to each bottlewith continued swirling. The bottles were swirled and shaken every 1-2minutes for 15 minutes. The contents gradually thickened. The bottleswere then purged with nitrogen, capped and placed in a 50° C.polymerizer for approximately 2.5 days.

The bottles were then removed from the polymerizer, cooled in water andopened. Following this procedure, the contents of the bottles were blowninto a five gallon kettle with nitrogen. The contents of the kettle werethen diluted with one gallon of hexane and stirred for 30 minutes. Theresultant slurry was filtered in 5 portions each washed with 700 cc ofhexane. The filter cakes were then placed in two large trays, broken upby hand and dried in a hood for 3 hours with frequent stirring. Thetrays were then placed in a vacuum oven operating at a temperature of65° C. and at 0.01 to 0.05 mm Hg for 40 hours. The resultant zincdimethacrylate in the form of a lightly caked powder was then broken upin a Waring blender and passed through a 50 mesh screen. Yield ofproduct was 1525.5 grams.

Analysis of the product for ash content showed it to contain 33.7% ashwhich compares to a theoretical ash content of 34.5%. The product wasalso subjected to differential thermal analysis (DTA). Procedures forobtaining DTA curves are well known and are described in instrumentmanufacturers' manuals and various texts. DTA of the product revealed amajor endotherm peaking at 177° C. and a minor endotherm peaking at 141°C.

EXAMPLE 2

To a 2-liter three-necked flask equipped with a stirrer, thermometer,nitrogen inlet and outlet was charged 792.0 grams of hexane, 99.0 gramsof zinc oxide, 0.3 grams of Ucar Super Wetter FP, a nonionic organosilicone surfactant available from Union Carbide, 0.3 grams of L-522, anonionic organo silicon surfactant also available from Union Carbide and0.3 grams of DC190, a silicone glycol copolymer surfactant availablefrom Dow Corning Corporation. The contents of the flask were stirred at250-300 RPM for 23 hours. Then, 204.6 grams of methacrylic acid wasadded to the flask with stirring continued. Prior to this addition, thecontents of the flask were at room temperature (i.e., 27° C.). However,within one minute after addition of the methacrylic acid, an exothermoccurred which caused the temperature to rise to 42° C. The temperatureof the reaction mixture slowly dropped reaching a temperature of 35° C.after 30 minutes. The reaction was continued with stirring for a totalof 18 hours. The resultant fluid suspension was filtered to recover thezinc dimethacrylate particles; the particles were then washed withhexane, resuspended in 600 cc of hexane, filtered again and washed withhexane. The filter cakes were then placed in trays, dried in a hood andvacuum dried using substantially the same procedure set forth inExample 1. The resultant zinc dimethacrylate in the form of a softpowder was then passed through a 50 mesh screen.

The product was analyzed for ash content and found to contain 34.36% ashwhich compares to a theoretical ash content of 34.5%.

EXAMPLE 3

To a 5-gallon openhead bucket equipped with a polypropylene liner,baffles placed between the liner and bucket, a high speed air motor withattached stirrer and thermometer was charged in sequence 12,000 cc ofhexane, 3.44 cc of Triton X-15, 3.4 cc of Triton X-45, 3.4 cc of TritonX-100, 1008 grams of zinc oxide and 2062 grams of methacrylic acid.(Triton X-15, X-45 and X-100 are nonionic octylphenoxy polyethoxyethanol surfactants available from Rohm & Haas Company). Followingaddition of the methacrylic acid, a polyethylene cover was placed overthe bucket to prevent loss of hexane by evaporation. The ingredientswere added with vigorous stirring. Prior to the addition of methacrylicacid, the temperature inside the bucket was 27° C. (i.e., roomtemperature). Within two minutes following the addition, an exothermoccurred which caused the temperature to rise to 44° C. The contents ofthe bucket were vigorously stirred for 8 hours at which time thetemperature had dropped to 40° C. The degree of stirring was reducedslightly and the reaction continued for an additional 15 hours (totalreaction time 23 hours) at which time the temperature had fallen to 36°C. As the reaction neared completion, the contents in the bucket took onthe form of a fluid suspension. The suspension was then removed from thebucket, filtered, and the recovered particles were washed, dried in ahood and in a vacuum oven (65° C., 0.08 mm Hg) as in Example 1. Theresultant zinc dimethacrylate in the form of a lightly caked powder wasthen broken up in a Waring blender and passed through a 50 mesh screen.

A sample of the product was analyzed and found to contain 33.6% ash.

This example was repeated several times and the product from each runwas combined. A sample of product from the combined runs was evaluatedand found to have a nitrogen surface area of 4.5 m² /g and a calculatedparticle size of 0.78 microns (see Explanatory Note). Nitrogen surfacearea was determined substantially in accordance with the procedure setforth in ASTM D3037, Method D which is titled: "Surface Area By MonosorbAnalyzer" with the significant exception that a degas temperature of100° C. was used instead of the 200° C. degas temperature specified inthe test (see Explanatory Note).

Explanatory Note: The above example corresponds to Example 3 ofApplication Ser. No. 421,012, the parent application of thisapplication. In Example 3 of the parent, the nitrogen surface area isreported as 2.44 m² /g and the calculated particle size is reported as1.45 microns. The reason for the discrepancy is that in Example 3 of theparent the exact procedure of ASTM D3037, Method D, which was initiallydeveloped to measure the surface area of carbon black and includes a200° C. degas temperature was utilized. However, since the filing of theparent application, the applicants have discovered that the 200° C.degas temperature causes a disruption of the surface area of zincdimethacrylate powder thereby resulting in lower surface area valuesthan are actual. However, the above results represent a retesting of thezinc dimethacrylate powder using the modified procedure.

EXAMPLE 4

To a 1-liter beaker equipped with a stirrer and thermometer was charged391 mililiters (ml) of hexane, 0.11 ml each of Triton X-15, Triton X-45and Triton X-100 and 32.8 grams of zinc oxide. (Triton X-15, X-45 andX-100 are nonionic octylphenoxy polyethoxy ethanol surfactants availablefrom Rohm & Haas Company). The mixture was stirred for 5 minutes and67.2 grams of methacrylic acid were then added to the beaker. Followingthis addition, stirring of the reaction mixture was continued for 23hours with the temperature being less than 35° C. The resultant fluidsuspension was filtered to recover the zinc dimethacrylate particleswhich were then pressed as dry as possible and air dried overnight.Final drying of the resultant zinc dimethacrylate powder was conductedin a vacuum oven at 60° C.

A sample of the zinc dimethacrylate powder obtained showed a nitrogensurface area of 5.35 m² /g. Nitrogen surface area was determined inaccordance with the modified ASTM D3037, Method D, procedure utilized inExample 3 (i.e., 100° C. degas temperature).

EXAMPLE 5

In this example, Example 4 was substantially repeated except thatadditional agitation was provided using ultrasound.

A sample of the resultant zinc dimethacrylate powder showed a nitrogensurface area of 4.98 m² /g using the modified surface area procedures ofExamples 3 and 4.

COMPARATIVE EXAMPLE A

In this example, the procedure of Chem Abstract Article87-5403--Kobayashi et al. (Japanese Kokai 76,138,616), one of theprincipal references cited against U.S. Application Ser. No. 421,012,the parent application to the present application, was evaluated.

The procedure employed to evaluate the Kobayashi et al. process was asfollows:

To a 1-liter flask equipped with stirrer and azeotrope trap with refluxcondenser was charged 391 ml toluene and 32.8 grams of zinc oxide. Thecontents of the flask were stirred and warmed to about 50° C. and then67.2 grams of methacrylic acid were added. A house vacuum line wasattached through the top of the condenser and enough vacuum was appliedto cause gentle refluxing. Reaction was terminated after 7 hours at 50°C. when no more water was collected in the azeotrope trays. The contentsof the flask were then filtered, the precipitate pressed as dry aspossible and air dried overnight. Final drying was conducted in a vacuumoven at 60° C.

The resultant zinc dimethacrylate in the form of a fine white powder hada nitrogen surface area of 3.1 m² /g as determined by the nitrogensurface area procedure of Examples 3-5.

COMPARATIVE EXAMPLES B & C

In these examples, the effects of a zinc dimethacrylate powder producedby the method of the invention (Example 4) and zinc dimethacrylatepowder produced by the method of Kobayashi et al. (Example A) on theproperties of a vulcanized synthetic rubber composition were evaluated.

The synthetic compositions employed to conduct the evaluations had thefollowing formulations:

    ______________________________________                                                           parts by weight                                            Example              B       C                                                ______________________________________                                        S1502.sup.(a)        100.0   100.0                                            Zinc Dimethacrylate of Ex. A                                                                       40.0    --                                               Zinc Dimethacrylate of Ex. 4                                                                       --      40.0                                             Vulcup R.sup.(b)     0.3     0.3                                              Polygard.sup.(c)     2.0     2.0                                              Total                142.3   142.3                                            ______________________________________                                         .sup.(a) a styrene/butadiene rubber containing 23.5% bound styrene            available from The Firestone Tire & Rubber Company.                           .sup.(b) bis(t-butylperoxy)diisopropyl benzene.                               .sup.(c) a tri(nonylated phenol) phosphate antioxidant available from         Uniroyal.                                                                

The above formulations were mixed on a cold two roll mill. The mixedcompounds were then cured and tested for stress-strain properties. Avisual examination of samples of the cured compounds revealed that thecompound of Example B (zinc dimethacrylate of Kobayashi, et al.) wasnearly opaque while that of Example C (zinc dimethacrylate of theinvention) was almost transparent. Test conditions and results are shownin the table.

                  TABLE                                                           ______________________________________                                        Example          B          C                                                 ______________________________________                                        Cure time (min)  20' at 160° C.                                                                    20' at 160° C.                             at temp. °C.                                                           Stress-strain                                                                 at 23° C.                                                              10% modulus, MPa 1.2        1.6                                               100% modulus, MPa                                                                              5.8        7.5                                               200% modulus, MPa                                                                              11.3       14.2                                              Tensile, MPa     12.8       15.1                                              Elongation at break, %                                                                         226        215                                               ______________________________________                                    

As can be seen from the above data, the vulcanized polymeric compositionof Example C which contains zinc dimethacrylate produced by the methodof the invention has much better stress-strain properties than Example Bwhich contains zinc dimethacrylate produced by the method of Kobayashiet al.

EXAMPLES 6-8

In these examples, vulcanizable polymeric compositions containing zincdimethacrylate produced in accordance with the procedures of Examples1-3 were prepared. Composition formulations were as follows:

    ______________________________________                                                    Ex. No.                                                           Ingredients   6          7       8                                            ______________________________________                                        Hevea (NR)    100.0      100.0   100.0                                        Zinc dimethacrylate                                                                         50.0.sup.(1)                                                                             50.0.sup.(2)                                                                          50.0.sup.(3)                                 Vulcup R.sup.(4)                                                                            1.0        1.0     1.0                                                        151.0      151.0   151.0                                        ______________________________________                                         .sup.(1) prepared in accordance with the procedure of Example 1               .sup.(2) prepared in accordance with the procedure of Example 2               .sup.(3) prepared in accordance with the procedure of Example 3               .sup.(4) bis(t-butyl peroxy)diisopropyl benzene                          

The above formulations were mixed on an electric mill with no externalheat added. The mixed formulations were cured and tested forstress-strain properties. Test conditions and properties are shown inTable I.

                  TABLE I                                                         ______________________________________                                        Ex. No.     6          7          8                                           ______________________________________                                        Cure time (min.)                                                                          20' at 160° C.                                                                    20' at 160° C.                                                                    20' at 160° C.                       at temp. °C.                                                           Stress-strain                                                                 at 23° C.                                                              10% modulus, MPa                                                                          2.5        3.4        2.7                                         300% modulus, MPa                                                                         14.6       17.1       18.2                                        Tensile, MPa                                                                              30.1       23.8       25.5                                        Elongation at Break                                                                       640        446        443                                         ______________________________________                                    

As will be evident from the above data, vulcanizable polymericcompositions of the invention containing zinc dimethacrylate produced bythe method of the invention exhibit excellent 300% modulus and tensilevalues.

COMPARATIVE EXAMPLES D & E

For comparative purposes, vulcanizable polymeric compositions, havingbasically the same formulations as in Examples 6-8, were prepared exceptthat a commercially available zinc dimethacrylate was substituted forthe zinc dimethacrylate prepared in accordance with the method of theinvention. This commercial zinc dimethacrylate was designated MPL #7742and was commercially available from Monomer Polymer Laboratories. Thiszinc dimethacrylate prior to use was vacuum dried to an ash content of34.9% and then evaluated for nitrogen surface area in accordance withthe modified ASTM D3037-78, Method D, procedure used in Examples 3-5.The nitrogen surface area of MPL #7742 by the modified procedure was0.960 m² /g. (Note: these examples correspond to Examples A and B of theparent application and the surface area of MPL #7742 reported thereinwas 0.73 m² /g by the original ASTM D3037-78, Method D procedure. Hencethe above 0.960 m² /g surface area value represents a retest of MPL#7742.)

Two formulations containing MPL #7742 were prepared at different timesand tested for stress-strain properties. Compositional formulationsdesignated Examples D and E and test results are shown in Table I(a).For convenience in comparing the stress-strain properties to thoseobtained by compositions of the invention, a vulcanizable polymericcomposition of the invention designated Control, previously prepared andtested, is also included in the Table.

                  TABLE I(a)                                                      ______________________________________                                        Ex. No.     Control    D          E                                           ______________________________________                                        Ingredients                                                                   Hevea (NR)  100.0      100.0      100.0                                       Zinc dimethacrylate                                                           source      Ex. 1      MPL #7742  MPL #7742                                   amount      50.0       50.0       50.0                                        Vulcup R    1.0        1.0        1.0                                         Total       151.0      151.0      151.0                                       Cure time (min.)                                                                          20' at 160° C.                                                                    20' at 160° C.                                                                    20' at 160° C.                       at temp. °C.                                                           Stress-strain                                                                 at 23° C.                                                              10% modulus, MPa                                                                          2.15       0.20       0.28                                        300% modulus, MPa                                                                         14.10      4.10       4.96                                        Tensile, MPa                                                                              23.80      13.40      13.34                                       Elongation at Break                                                                       519        770        692                                         ______________________________________                                    

As can be seen from the above data, the compositions containing the MPL#7742 zinc dimethacrylate (nitrogen surface area 0.960) exhibitdramatically lower modulus and tensile values than the Control exampleor Examples 6-8. Note particularly the difference between the modulusand tensile values of Examples D and E and Example 8 which contains zincdimethacrylate having a nitrogen surface area of 4.5 m² /g.

The following examples, (i.e., 9-35) further illustrate vulcanizablecompositions of the invention containing zinc dimethacrylate prepared bythe process of Example 1.

EXAMPLES 9-14

In these examples, vulcanizable polymeric compositions containingvarious rubbery polymers were prepared. Composition formulations were asfollows:

    ______________________________________                                                Parts by Weight                                                              Example No.                                                            Ingredients                                                                            9       10      11    12    13    14                                 ______________________________________                                        EPDM.sup.(a)                                                                           100.0   --      --    --    --    --                                 FRN510.sup.(b)                                                                         --      100.0   --    --    --    --                                 Hevea (NR)                                                                             --      --      100.0 --    --    --                                 Neoprene --      --      --    100.0 --    --                                 GN                                                                            S1502.sup.(c)                                                                          --      --      --    --    100.0 --                                 EPR.sup.(d)                                                                            --      --      --    --    --    100.0                              Zinc di- 50.0    50.0    50.0  50.0  50.0  50.0                               methacrylate                                                                  Vulcup R.sup.(e)                                                                       1.0     1.0     1.0   1.0   1.0   1.0                                Total    151.0   151.0   151.0 151.0 151.0 151.0                              ______________________________________                                         .sup.(a) an ethylene/propylene/diene terpolymer having a Mooney viscosity     ML.sub.4 /257° F., of 55 available from Copolymer Corporation unde     the designation EPSyn 55.                                                     .sup.(b) a nitrile rubber containing 32% acrylonitrile.                        .sup.(c) a styrene/butadiene rubber containing 23.5% bound styrene           available from The Firestone Tire & Rubber Company.                           .sup.(d) a saturated ethylene/propylene rubber available from the B. F.       Goodrich Company under the designation EPCAR306.                              .sup.(e) bis(t-butyl peroxy)diisopropyl benzene.                         

The above formulations were mixed on an electric mill with no externalheat added. The mixed formulations were cured and then tested forstress-strain properties. Test conditions and properties are shown inTable II.

                  TABLE II                                                        ______________________________________                                        Example No.                                                                            9       10      11    12    13    14                                 ______________________________________                                        Cure time                                                                              15' at  15' at  15' at                                                                              15' at                                                                              15' at                                                                              30' at                             (min.) at                                                                              160° C.                                                                        160° C.                                                                        160° C.                                                                      160° C.                                                                      160° C.                                                                      160° C.                     temp. °C.                                                              Stress-strain                                                                 at 23° C.                                                              10% modulus,                                                                           1.6     3.7     1.4   2.2   5.1   1.5                                MPa                                                                           200% modu-                                                                             --      19.1    --    --    24.6  --                                 lus, MPa                                                                      300% modu-                                                                             10.0    --      8.9   11.5  --    9.8                                lus, MPa                                                                      Tensile, MPa                                                                           23.2    19.8    20.2  16.3  24.4  17.1                               Elongation at                                                                          615     210     600   460   195   447                                Break, %                                                                      Stress-strain                                                                 at 100° C.                                                             10% modulus,                                                                           2.1     --      1.5   2.3   3.6   --                                 MPa                                                                           200% modu-                                                                             --      --      --    --    --    --                                 lus, MPa                                                                      300% modu-                                                                             11.5    --      7.2   11.8  --    --                                 lus, MPa                                                                      Tensile, MPa                                                                           17.3    --      16.7  12.5  14.4  --                                 Elongation at                                                                          479     --      720   330   150   --                                 Break, %                                                                      ______________________________________                                    

As the above data illustrates, vulcanizable polymeric compositions ofthe invention exhibit high modulus, tensile and elongation when cured.In comparison, a conventional sulfur-curable rubber compound containinga solution styrene/butadiene copolymer having 18% bound styrene, 37.5parts extender oil, 63 parts HAF black, 1.8 parts sulfur and 2.1 partsof a sulfenamide-type accelerator on curing tested at room temperaturehas a 10% modulus of 0.44 MPa, a 300% modulus of 6.1 MPa, a tensile of18.4 MPa, and an elongation at break of 738%.

EXAMPLES 15-18

In these examples, vulcanizable polymeric compositions containing blendsof rubbery polymers were prepared. Composition formulations were asfollows:

    ______________________________________                                                    Parts by Weight                                                              Example No.                                                        Ingredients  15       16       17     18                                      ______________________________________                                        Hevea (NR)   50.0     50.0     --     --                                      EPDM*        50.0     --       50.0   50.0                                    S1502        --       50.0     50.0   --                                      FRN510       --       --       --     50.0                                    Zinc dimethacrylate                                                                        50.0     50.0     50.0   50.0                                    Vulcup R     1.0      1.0      1.0    1.0                                     Total        151.0    151.0    151.0  151.0                                   ______________________________________                                         *EPDM of Example 9.                                                      

The above formulations were mixed, cured and tested for stress-strainproperties in accordance with the procedure of Examples 6-8. Testconditions and properties are shown in Table III.

                  TABLE III                                                       ______________________________________                                        Example No.  15       16       17     18                                      ______________________________________                                        Cure         15' at   15' at   15' at 15' at                                               160° C.                                                                         160° C.                                                                         160° C.                                                                       160° C.                          Stress-strain                                                                 at 25° C.                                                              10% modulus, MPa                                                                           2.8      2.7      4.2    2.4                                     200% modulus, MPa                                                                          --       --       16.7   --                                      300% modulus, MPa                                                                          10.2     17.7     --     9.0                                     Tensile, MPa 21.4     21.0     17.2   18.3                                    Elongation at                                                                              660      360      208    629                                     Break, %                                                                      Stress-strain                                                                 at 100° C.                                                             10% modulus, MPa                                                                           1.7      2.3      3.0    1.7                                     200% modulus, MPa                                                                          --       --       --     --                                      300% modulus, MPa                                                                          6.0      12.2     --     7.0                                     Tensile, MPa 9.5      12.2     9.2    8.7                                     Elongation at                                                                              543      298      119    393                                     Break, %                                                                      ______________________________________                                    

The above data indicates that the compositions containing blends ofrubbery polymers are well cured and exhibit excellent strength. Ofparticular interest, the composition containing the blend of EPDM andnitrile rubber (Example 18) polymers which are normally incompatible,also cured well and exhibited good properties.

EXAMPLES 19-24

In these examples, vulcanizable polymeric compositions containingvariable quantities of zinc dimethacrylate were prepared. Compositionformulations were as follows:

    ______________________________________                                                Parts by Weight                                                              Example No.                                                            Ingredients                                                                            19      20      21    22    23    24                                 ______________________________________                                        S1502    100.0   --      --    --    --    --                                 Natural  --      100.0   100.0 --    --    --                                 rubber                                                                        (pale crepe)                                                                  EPDM*    --      --      --    100.0 100.0 100.0                              Zinc di- 30.0    60.0    70.0  60.0  70.0  80.0                               methacrylate                                                                  Vulcup R 1.0     1.0     1.0   1.0   1.0   1.0                                Total    131.0   161.0   171.0 161.0 171.0 181.0                              ______________________________________                                         *An ethylene/propylene diene terpolymer having a Mooney viscosity of          ML.sub.4 /257° F. of 40 available from Copolymer Corporation under     the designation EPSyn 40A.                                               

The above formulations were mixed, cured and tested for stress-strainproperties in accordance with the procedure of Examples 6-8. Testconditions and properties are shown in Table IV.

                  TABLE IV                                                        ______________________________________                                        Example No.                                                                            19      20      21    22    23    24                                 ______________________________________                                        Cure     20' at  15' at  15' at                                                                              15' at                                                                              15' at                                                                              15' at                                      160° C.                                                                        160° C.                                                                        160° C.                                                                      160° C.                                                                      160° C.                                                                      160° C.                     Stress-strain                                                                 at 25° C.                                                              10% modulus,                                                                           0.58    3.2     4.6   2.2   3.5   4.8                                MPa                                                                           300% modu-                                                                             11.1    14.6    17.2  9.8   14.0  18.7                               lus, MPa                                                                      Tensile, MPa                                                                           13.6    26.8    25.3  25.9  27.1  25.9                               Elongation at                                                                          349     585     486   747   584   428                                Break, %                                                                      Stress-strain                                                                 at 100° C.                                                             10% modulus,                                                                           --      2.3     3.1   1.8   2.4   3.5                                MPa                                                                           300% modu-                                                                             --      8.9     10.1  7.7   9.7   12.7                               lus, MPa                                                                      Tensile, MPa                                                                           --      14.6    14.0  12.7  13.0  14.9                               Elongation at                                                                          --      568     467   530   426   369                                Break, %                                                                      ______________________________________                                    

The room temperature (25° C.) tensile data from Examples 20-24 indicatestest compositions containing high levels (e.g., 60-80 parts) of zincdimethacrylate have tensile strengths (i.e., 25.3-27.1 MPa) approachingthose of some commercial polyurethanes. For example, a polyurethanecomposition composed of Adiprene L-367, a polyurethane prepolymeravailable from duPont, and Caytur 21 a salt complex of methylenedianaline available from duPont, when cured for 1 hour at 120° C.exhibits a tensile strength at 25° C. of 27.8 MPa.

EXAMPLES 25-27

In these examples, vulcanizable polymeric compositions containingvarying amounts of peroxide curing agents were prepared. Compositionformulations were as follows:

    ______________________________________                                                     Parts by Weight                                                              Example No.                                                       Ingredients   25         26      27                                           ______________________________________                                        S1502         100.0      100.0   100.0                                        Zinc dimethacrylate                                                                         50.0       50.0    50.0                                         Vulcup R      1.0        0.5     0.2                                          Total         151.0      150.05  150.02                                       ______________________________________                                    

The above formulations were mixed, cured and tested for stress-strainproperties as in Examples 6-8. Test conditions and properties are shownin Table V.

                  TABLE V                                                         ______________________________________                                                     Stress-strain (MPa)                                              Example                                                                              Cure at 160° C.                                                                             300%        Elong-                                No.    Time (min.) 10% mod  mod   Tensile                                                                             ation %                               ______________________________________                                        25      10'        5.0      --    21.5  165                                          20          8.4      --    13.5   36                                   26     10          3.0      19.0  20.1  322                                          20          5.2      --    19.5  138                                   27     20          3.0      19.7  21.9  345                                          30          3.6      23.8  22.2  278                                   ______________________________________                                    

EXAMPLES 28-31

In these examples, vulcanizable polymeric compositions containing addedreinforcing fillers were prepared. Composition formulations were asfollows:

    ______________________________________                                                    Parts by Weight                                                              Example No.                                                        Ingredients  28       29       30     31                                      ______________________________________                                        S1502        100.0    100.0                                                   Natural rubber                                                                             --       --       100.0  100.0                                   Zinc diamethacrylate                                                                       65.0     37.5     65.0   50.0                                    HAF black    5.0      12.5     5.0    25.0                                    Vulcup R     0.2      0.2      1.0    1.0                                     Total        170.2    150.2    171.0  176.0                                   ______________________________________                                    

The above formulations were mixed on a mill, cured and tested forstress-strain properties. Cure conditions, test conditions andproperties are shown in Table VI.

                  TABLE VI                                                        ______________________________________                                        Example No.  28       29       30     31                                      ______________________________________                                        Cure         20' at   20' at   30' at 30' at                                               160° C.                                                                         160° C.                                                                         160° C.                                                                       160° C.                          Stress-strain                                                                 at 25° C.                                                              10% modulus, MPa                                                                           3.2      1.1      3.8    3.0                                     300% modulus, MPa                                                                          15.7     9.0      22.4   20.6                                    Tensile, MPa 19.1     20.2     22.2   22.5                                    Elongation at                                                                              398      721      301    339                                     Break, %                                                                      ______________________________________                                    

EXAMPLES 32-35

In these examples, vulcanizable polymeric compositions containing 50parts HAF and variable quantities of zinc dimethacrylate were prepared.The effect of zinc dimethacrylate on hysteresis properties was evaluatedusing a conventional shear modulus test. In the shear modulus test, G'represents shear modulus, G" represents shear modulus loss and Tan isthe ratio of shear modulus to shear modulus loss. Tan is regarded as anindication of hysteresis properties with low values indicating lowerhysteresis and higher values indicating higher hysteresis. Thecompositions were mixed on a mill and cured and evaluated for shearmodulus at low strain. Composition formulations, cure conditions, testconditions and shear modulus results are shown in Table VII.

                  TABLE VII                                                       ______________________________________                                        Example No.  32       33       34     35                                      ______________________________________                                        Ingredients                                                                   S1502        100.0    100.0    100.0  100.0                                   HAF black    50.0     50.0     50.0   50.0                                    Zinc dimethacrylate                                                                        50.0     40.0     30.0   20.0                                    Vulcup R     0.2      0.2      0.2    0.2                                     Total        200.2    190.2    180.2  170.2                                   Cure at 160° C. (min.)                                                              30       30       30     30                                      Test temperature, °C.                                                               75       75       75     75                                      Shear Modulus                                                                 10% strain,                                                                   G' Mpa       4.14     3.49     2.64   1.64                                    G"           0.69     0.59     0.46   0.32                                    Tan          0.168    0.169    0.174  0.195                                   ______________________________________                                    

The above data indicates that with increasing amounts of zincdimethacrylate at constant black loading, the modulus of the compoundsignificantly increases while the Tan values are decreasing. This wouldappear to indicate a lower hysteresis property at higher modulus whichis an ususual and unexpected result.

We claim:
 1. Vulcanizable polymeric compositions comprising:(a) rubberypolymers selected from the group consisting of natural rubber,ethylene/propylene copolymers, ethylene/propylene/diene terpolymers,styrene/butadiene copolymers, nitrile rubbers, neoprene and blendsthereof; (b) from about 25 to about 85 parts by weight per 100 parts byweight of said rubbery polymers of a zinc dimethacrylate having asurface area of from about 3.7 to about 5.4 m² /g; and (c) a cureeffective amount of a peroxide curing agent.
 2. The composition of claim1 wherein said rubbery polymer is natural rubber.
 3. The composition ofclaim 1 wherein said rubbery polymer is an ethylene/propylene/dienemonomer terpolymer.
 4. The composition of claim 1 wherein said rubberypolymer is a styrene/butadiene copolymer.
 5. The composition of claim 1wherein said rubbery polymer is a nitrile rubber.
 6. The composition ofclaim 1 wherein said blend is a 50:50 blend of natural rubber and anethylene/propylene/diene/monomer terpolymer.
 7. The composition of claim1 wherein said blend is a 50:50 blend of natural rubber and astyrene/butadiene copolymer.
 8. The composition of claim 1 wherein saidblend is a 50:50 blend of a styrene/butadiene copolymer and anethylene/propylene/diene monomer terpolymer.
 9. The composition of claim1 wherein said blend is a 50:50 blend of an ethylene/propylene/dienemonomer terpolymer and nitrile rubber.
 10. The composition of claim 1wherein said zinc dimethacrylate is present in an amount of from 50 to80 parts by weight per 100 parts by weight of said rubbery polymers. 11.The composition of claim 1 wherein said peroxide curing agent isbis-(t-butyl peroxy)diisopropyl benzene.
 12. The composition of claim 1wherein said peroxide curing agent is present in an amount of from about0.2 to about 2.0 parts by weight per 100 parts by weight of rubberypolymer.
 13. The composition of claim 1 further comprising from about 5to about 60 parts by weight of a reinforcing agent or filler.
 14. Thecomposition of claim 13 wherein said reinforcing agent is carbon black.